Catalytic system for hydroconversion of naphtha

ABSTRACT

A hydroconversion catalyst for hydrodesulfurizing feedstock while preserving octane number of the feedstock includes a support having a mixture of zeolite and alumina, the zeolite having an Si/Al ratio of between about 1 and about 20, and an active phase on the support and including a first metal selected from group 6 of the periodic table of elements, a second metal selected from the group consisting of group 8, group 9 and group 10 of the period table of elements and a third element selected from group 15 of the periodic table of elements. A hydroconversion process is also disclosed.

CROSS REFERENCE

The instant application is a divisional of U.S. application Ser. No.09/932,297 filed on Aug. 17, 2001, which is currently pending.

BACKGROUND OF THE INVENTION

The invention relates to a catalytic system which is advantageous inhydroconversion of hydrocarbon feeds such as naphtha.

Many nations have implemented environmental legislation and energyconservation policies which idealize stringent rules in order todrastically reduce emissions of contaminants such as sulfur.

Clean air act amendments and other legislation have mandated reductionsin emission levels in terms of sulfur, olefins, aromatics and the like,which are considered to contribute to contamination levels.

One source of volume to the gasoline pool is naphtha, particularly FCCnaphtha, which is the source of approximately 80% of the sulfur in thegasoline pool. Further, such FCC naphtha also constitutes approximately40% (vol) of the total amount in the gasoline pool.

Clearly, FCC naphtha is an important feed to be treated for reduction ofsulfur.

Various hydroconversion processes have been developed for treating suchfeedstocks in order to reduce sulfur content thereof. One such processinvolves a first stage wherein sulfur and nitrogen are substantiallyremoved, but also wherein olefins contained in the feedstock are greatlysaturated. In such processes, the saturation of olefins results in aloss in octane values, and a second stage treatment is employed in orderto recuperate the lost octane values.

In the reformulation of gasoline, an octane loss is expected to occurdue specifically to hydrogenation of olefins (HDO). This loss iscompensated or recovered through cracking reactions, isomerization,aromatization, and the like, which can be accomplished during theaforesaid second stage of the reaction.

Hydroconversion catalysts are conventionally sensitive to nitrogen inthe feed, and can require pre-treatment of the feed to remove nitrogen,which also adds a step and additional cost to the preparation process.

Of course, any required second stage or step adds to the processing costfor fractions such as naphtha, and therefore the need exists forimproved methods of reduction in sulfur and nitrogen content withoutadverse impact on octane values (RON, MON).

It is therefore the primary object of the present invention to provide acatalyst and process for using same whereby the need for additionalreaction zones is avoided.

It is a further object of the present invention to provide a catalystand process for using same wherein hydrodesulfurization andhydrodenitrification are accomplished.

It is a still further object of the invention to provide a catalystwhich is resistant to nitrogen and can avoid the need for pre-treatmentto remove nitrogen from the feed.

Other objects and advantages of the present invention will appear hereinbelow.

SUMMARY OF THE INVENTION

In accordance with the present invention, the foregoing objects andadvantages have been readily attained.

According to the invention, a hydroconversion catalyst is provided whichis effective in hydrodesulfurizing feedstocks while preserving octanenumbers, which catalyst comprises a support comprising a mixture ofzeolite and alumina, said zeolite having an Si/Al ratio of between about1 and about 20, and an active phase on said support and comprising afirst metal selected from group 6 of the periodic table of elements, asecond metal selected from the group consisting of group 8, group 9 andgroup 10 of the periodic table of elements, and a third element selectedfrom the group 15 of the periodic table of elements.

In further accordance with the present invention, a process forhydroconversion of hydrocarbon feedstock is provided, which processcomprises providing a hydrocarbon feed having an initial sulfur contentand an initial olefin fraction; providing a hydroconversion catalystcomprising a support comprising a mixture of zeolite and alumina, saidzeolite having an Si/Al ratio of between about 1 and about 20, and anactive phase on said support and comprising a first metal selected fromgroup 6 of the periodic table of elements, a second metal selected fromthe group consisting of group 8, group 9 and group 10 of the periodictable of elements, and a third element selected from the group 15 of theperiodic table of elements, and exposing said feed to said catalystunder hydroconversion conditions so as to provide a product having afinal sulfur content less than said initial sulfur content. The olefincontent of the final product varies depending upon the operatingconditions used to process the feedstocks. In some cases, the olefinretention is very high and for other cases, the olefin content issubstantially lower than the initial olefin content. Advantageously,however, the catalyst of the present invention provides for increasedratio of iso-paraffins to n-paraffins and reduction in molecular weightof the n-paraffins which serve to improve octane ratings of the productand help make up for the olefin loss which itself is reduced in anyevent.

BRIEF DESCRIPTION OF DRAWINGS

A detailed description of preferred embodiments of the present inventionfollows, with reference to the attached drawings, wherein:

FIG. 1 illustrates the relationship between carbon atoms of varioushydrocarbon fractions and research octane number (RON);

FIG. 2 illustrates the relationship between process temperature andaverage molecular weight for several feedstocks and for processescarried out utilizing different types of catalysts; and

FIG. 3 illustrates the relationship between Delta Octane (Delta Road)and HDS (Hydrodesulfurization) activity for different types ofcatalysts.

DETAILED DESCRIPTION

The invention relates to a catalyst and catalyst system forhydroconversion of hydrocarbon feedstocks such as naphtha, and providesfor reduction of sulfur in naphtha feedstock cuts without substantialreductions in octane values, which is common with hydrotreating usingconventional catalysts.

The octane value of a particular hydrocarbon fraction such as naphthafractions and the like has been found to depend upon the number ofcarbon atoms in the various hydrocarbon fractions contained therein. Oneimportant fraction is the olefin fraction, and this fraction has beenfound to be extremely susceptible to hydrogenation when subjected toconventional hydrodesulfurization (HDS) catalysts. The result is thatvarious gasoline pool additives such as naphtha, which must be treatedwith HDS catalysts, have reduced octane values and require a secondtreatment stage for recuperating the octane value.

FIG. 1 shows a relationship between research octane number (RON) and thenumber of carbon atoms for various hydrocarbon fractions of a typicalgasoline pool fraction. As shown, the RON value decreases substantiallyas the number of carbon atoms for each fraction, including the olefins,increases.

In accordance with the present invention, a catalyst system has beendevised which advantageously provides for excellent HDS activity, andwhich also provides excellent hydroconversion activity, and which avoidsthe substantial decreases in octane values which are caused byconventional hydrotreating catalyst systems. In addition, the catalystsystem of the present invention is tolerant to nitrogen, and cantherefore be used in a single treatment stage or reactor for treatingfeedstocks having sulfur, nitrogen and the like, and provides a productwith substantially reduced sulfur and nitrogen content with octanevalues either unchanged or reduced slightly, and in some cases improved.

In accordance with the present invention, the catalyst system includes asupport component and an active phase on the support component. Thesupport component in accordance with the present invention is preferablya silicon and aluminum structure such as zeolite, aluminosilicate,silica and alumina mixtures, and the like. In accordance with thepresent invention, it has been found that excellent HDS activity, withtolerance to nitrogen and also good HDN activity, can be accomplishedwith substantial hydroconversion activity so long as the ratio ofsilicon to aluminum in the zeolite is between about 1 and about 20. TheSi/Al ratio is critical in that higher ratios result in poorhydroconversion activity and resulting loss in octane values. It ispreferred that the zeolites have an Si/Al ratio less than about 15, andmore preferably less than about 12. ST-5 zeolite having an Si/Al ratioof 11.7 is particularly well suited to the present invention.

The support is preferably a mixture of zeolite and alumina, andpreferred zeolite is MFI zeolite, most preferably ST-5 zeolite as setforth above. Suitable ST-5 zeolite is disclosed in U.S. Pat. No.5,254,327. Such a zeolite can be combined with appropriate amounts ofalumina to provide the desired acid catalysis. Such a zeolite has beenfound to provide excellent selective cracking and isomerizationactivities while avoiding octane loss.

The active metal phase to be deposited on or otherwise provided alongwith the support preferably includes a first metal selected from group 6(CAS group VIB) of the periodic table of elements, most preferablymolybdenum. The active metal phase also includes a second metalpreferably selected from the group consisting of group 8, group 9 andgroup 10 (CAS group VIII) of the periodic table of elements, preferablynickel, cobalt or mixtures thereof, most preferably cobalt, and a thirdelement selected from group 15 (CAS VA) of the periodic table ofelements, most preferably phosphorus.

In accordance with the present invention, the catalyst preferablyincludes metal active phase having at least about 1% (wt) of the firstmetal (group 6), at least about 0.5% (wt) of the second metal (groups 8,9 and 10), and at least about 0.2% (wt) of the third element (group 15).More preferably, the catalyst includes the first metal, preferablymolybdenum, in an amount between about 2 and about 15% (wt), the secondmetal, preferably nickel or cobalt, in an amount between about 0.5and/or about 8.0% (wt), and the third element, preferably phosphorus, inan amount between about 0.5 and about 5.0% (wt). This combination ofactive metals and elements for a support as described above has beenfound in accordance with the present invention to provide the desiredHDS and HDN activity along with other activity that compensates forolefin hydrogenation (HDO) so as to provide a final product havingacceptable octane values.

As demonstrated in the Examples, the catalyst according to the presentinvention advantageously provides for increase in molar ratio ofiso-paraffin to n-paraffin, and also reduces molecular weight of then-paraffin fraction, both of which improve octane values of the finalproduct and thereby substantially compensate for the HDO activity of thecatalyst.

In accordance with the present invention, the acidity of the catalysthas also been found to be important in connection with the desiredtolerance to nitrogen and acid catalyst activity such as selectivecracking and isomerization reactions.

A suitable catalyst in accordance with the present invention can beprepared using known techniques, and following processes well known to aperson of ordinary skill in the art. The zeolite is preferably mixedwith alumina under protonic form, and both in powder form, and thezeolite and alumina are preferably mixed at a proportion of betweenabout 10 and about 90% (wt) zeolite and between about 90 and about 10%(wt) alumina. To the mixture of zeolite and alumina, a peptizing agentmay also be added such as, for example, acetic acid and the like,preferably in amounts of between about 0.5 and about 3.0% (wt), and theresulting mixture is a paste which is extruded into appropriate forms,such as, for example, {fraction (1/16)}″ extrudates. The extrudates arethen dried, preferably at room temperature, and then at a temperature of120° C., and the dried extrudates are then calcined, for example at atemperature of about 550° C. for approximately 2-4 hours. Calcinationmay preferably be carried out at a heating velocity of 60° C. increasesper hour, until the desired temperature is reached.

After calcination, the extrudates are preferably impregnated with thegroup 15 active element (preferably phosphorus), and the group 6 activemetal (preferably molybdenum). After this impregnation step, theimpregnated extrudates are dried, for example using the same procedure,preferably at room temperature and then a temperature of about 120° C.,and after drying, the extrudates are further impregnated with the metalof group 8, 9 or 10, preferably nickel and/or cobalt, so as to completethe active metal phase impregnation onto the support structure. Ofcourse, the catalyst may be impregnated in different ways, as well, andcan be prepared using any known technique or process.

The impregnated extrudates are then dried again at room temperaturefollowed by 120° C., calcined at approximately 550° C. for a sufficientperiod of time and at a heating velocity at set forth above, and thecatalyst is then complete.

The catalyst may also be prepared by co-extruding the zeolite, aluminaand active metals. The extrudates are formed and impregnated at the sametime, and are dried and then calcined using a similar process asdescribed above.

Before use, the catalyst may be subjected to activation,pre-sulfurization, and other steps which are known to a person ofordinary skill in the art, at which time the catalyst is ready for usein processes for hydroconversion in accordance with the presentinvention.

A particularly suitable feedstock with which the catalyst of the presentinvention is useful is a naphtha feedstock, preferably anon-hydrotreated FCC naphtha (C9+) having at least about 5% (wt) ofolefins, such as that which can be obtained from the Amuay or from otherrefineries, for example. The typical characteristics of such acomposition are as set forth in Table 1 below.

TABLE 1 Contents Composition (% weight) Paraffins 3.09 Isoparaffins 12.2Olefins 8.6 Naphthenes 10.3 Aromatics 61.6 Non-identified, C13+ 1.7Sulfur 1930 ppm Nitrogen  186 ppm

Of course, the catalyst in accordance with the present invention canadvantageously be used with a wide variety of feedstocks, and the feedset forth in Table 1 is merely an example of a suitable feed. Theparticularly desirable characteristics of feed which are suitable fortreatment with the catalyst of the present invention, however, include afeed which requires at least HDS, and optionally HDN as well, whichincludes an olefin fraction, and which is to be incorporated into thegasoline pools. The feedstock can further contain at least about 1 ppmweight of nitrogen. With such a feedstock, the catalyst of the presentinvention advantageously serves to provide HDS and HDN activity withexcellent hydroconversion activity.

In accordance with the present invention, the process for treating sucha feedstock with the catalyst of the present invention includesproviding the suitable catalyst and feedstock, and exposing thefeedstock to the catalyst at hydroprocessing conditions including atemperature of between about 230° C. and about 450° C., a pressure ofbetween about 100 psi and about 1000 psi, a space velocity (LHSV)between about 0.5 h⁻¹ and about 20.0 h⁻¹, and a hydrogen/feedstock ratioof between about 100 and about 650 Nv/v.

In this regard, the catalyst of the present invention can advantageouslybe provided in a single reactor, or in two or more reactors, usingdifferent configurations between them, if desired, or in combinationwith other catalysts designed to provide other activity which may bedesirable for the particular feedstock, or out of the same feedstock, inquestion. It is particularly advantageous, however, that the catalyst ofthe present invention allows the desired results to be obtained in asingle reactor.

The feedstock so treated will have an initial sulfur content and aninitial olefin fraction, as well as, typically, an initial nitrogencontent. The resulting product will have a substantially reduced sulfurcontent, preferably a substantially reduced nitrogen content, and willhave a substantially reduced olefin content when desired, or a differentdesired olefin retention depending upon operation conditions used,without the decrease in octane values which is common when hydrotreatingusing conventional catalyst.

The process can be carried out utilizing multiple beds, either in thesame reactor or in different reactors. In addition, it has been foundthat the process temperature for use of the present catalyst ispreferably a temperature of between about 250° C. and about 410° C., andthat higher temperatures can result in liquid yield loss.

As will be demonstrated in the examples set forth below, the catalyst ofthe present invention provides for excellent HDS activity, withtolerance to the presence of nitrogen and HDN activity as well, adesired HDO activity, and advantageously provides for highhydroconversion activity thereby reducing the adverse impact on octanevalues which is currently experienced utilizing conventionalhydrotreating catalyst.

Due to the nitrogen tolerance and good hydroconversion activity, thecatalyst of the present invention can advantageously be used in a singlereactor process where the final product has acceptable sulfur content,and does not need octane value recuperation, and further where thecatalyst is not rapidly deactivated and no pre-treatment for nitrogen isneeded.

The following examples demonstrate the effectiveness of the catalyst ofthe present invention for use in treatment of naphtha feedstocks. Thisdata was obtained utilizing high pressure plants having 10-40 CCcapacity reactors, and using the following general methodology.

A determined volume of dried catalyst is fed to a stainless steelreactor having a length of 43 cm and an internal diameter of 3.5 cm. Apresulfurized feed is prepared by adding 0.9 cc of carbondisulfide ordimethyldisulfide (DMDS) (1.5% v/v) for each 60 cc of naphtha. Thecatalyst bed is activated and/or presulfurized utilizing thispresulfurized feed under the following operating conditions.

For 40 cc of Catalyst:

-   Pressure: 400 PSIG-   H₂ Flow: 195 cc/min-   Presulfurizing feedstock flow: 25.6 cc/h-   Temperatures: 159° C.(1 h) 240° C.(1 h) 280° C.(2 h)    For 30 cc of Catalyst:-   Pressure: 400 PSIG-   H₂ Flow: 146 cc/min-   Presulfurizing feedstock flow: 19.2 cc/h-   Temperatures: 150° C.(1 h) 240° C.(1 h) 280° C.(2 h)    For 20 cc of Catalyst:-   Pressure: 400 PSIG-   H₂ Flow: 97.33 cc/min-   Presulfurizing feedstock flow: 12.8 cc/h-   Temperatures: 150° C.(1 h) 240° C.(1 h) 280° C.(2 h)    For 10 cc of Catalyst:-   Pressure: 400 PSIG-   H₂ Flow: 36 cc/min-   Presulfurizing feedstock flow: 6.4 cc/h-   Temperatures: 150° C.(1 h) 240° C.(1 h) 280° C.(2 h)

In all cases, the LHSV is 0.641/h and H₂/feedstock relation is 365 Nv/v.Activation temperatures are utilized so as to provide a final value of330° C. or 280° C. depending on the process requirements.

After catalyst activation, the catalytic evaluations were carried out.The typical operational conditions used, at bench scale, weretemperatures between 280 and 380° C., fixed pressure of 600 psig, spacevelocity between 1 and 3 h⁻¹ and H₂/feedstock relation of 440 Nv/v.

EXAMPLE 1

10 cc of a commercial hydrotreatment catalyst (HDT1) containing Ni, Mo,and P (18% wt) supported on alumina were activated at 280° C. andevaluated according to the methodology described above, using an FCCC9+naphtha from the Amuay Refinery. The results are shown in Table 2.

TABLE 2 Feedstock Conventional Catalyst, FCC C9+ Naptha HDT1 NiMoP/Al₂O₃from Amuay Operation Conditions LSHV, h¹ 1 1 1 1 Pressure, psig 600 600600 600 Temperature, ° C. 300 320 340 360 Hours 7 12 15 20 ProductQuality Sulfur, ppm 153 52 45 43 1930 Nitrogen, ppm 12 <5 <5 <5 186Olefins, wt % 0.623 0.620 0.615 0.512 8.610 i-p/n-p ratio* 3.10 3.123.10 3.12 3.14 Average Molecular weight 136.0 135.8 135.7 135.7 137.5 ofn-paraffins HDS, wt % 92.1 97.3 97.8 97.8 HDN, wt % 93.5 >97 >97 >97*isoparaffins/normal paraffins ratio

A high hydrogenating activity toward olefins (HDO between 93.0 and 94.2%wt) is obtained. The HDS activity (hydrodesulfurization), as expected,increases with the temperature from 92.1 through 97% in weight and in asimilar way the HDN (hydrodenitrogenation) varies between 93.5 and morethan 97% in weight when the temperature increases from 300 to 360° C.However, the average molecular weight of n-paraffins is very close tothe average molecular weight of n-paraffins in the feedstock, indicatingthat the acid catalysis is very poor.

EXAMPLE 2

Commercial dispersible alumina B (Condea™) is mixed with an MFI zeolite(ST-5) containing a ratio Si/Al of 11.7 under protonic form (seechemical composition in Table 3), both powder, in a proportion of 50%(wt) ST-5 and 50% (wt) alumina.

TABLE 3 Chemical nA1 Crystal Surface MFI Zeolite Formula (10²⁰/g) size(μm) Area (m²/g) ST-5 Na_(0.23)H_(7.38)Si_(88.4) O₁₉₂ 7.5 0.8 332*nA1(10²⁰/g): Number of total Bronstad sites calculated from chemicalformula and Avogadro number (6.02 × 10²³)

In the mixing process of both solids, 2.5% weight of acetic acid isadded, in a proportion or ratio of 2.4 grams of solid per ml of acid.After mixing the solid is passed through a double extrusion press-mixeruntil the material is homogenized. After this mixture, extrusion is madeof the paste so as to form {fraction (1/16)}″ extrudates.

The extrudates are dried at room temperature. They are submittedafterwards to a temperature of 120° C. After drying, they are calcinedat 550° C. in a furnace for at least 2 more hours. In order to reachthis temperature, a heating velocity is used at 60° C. per hour. Aftercalcination, a humidity scale is used to determine the volume ofhydration with that of the volume of the solution of ammoniumheptamolybdate plus 85% (wt) of phosphoric acid, which will be used inimpregnation. The amounts of ammonium heptamolybdate and phosphoric acidare determined and selected to deposit in the final catalyst 12-13%weight of molybdenum and 2.7-3.0% weight of phosphorus.

After this impregnation, the extrudates are dried at room temperatureand at 120° C. After drying, the humidity scale is used to determine thevolume of nickel nitrate solution needed to deposit in the finalcatalyst 2.1-2.3% weight of nickel, and the impregnation is carried out.

Finally, the extrudates are dried once more at room temperature and at120° C., and then calcined at 550° C. during 2 hours using the sameheating velocity of 60° C./hour. This catalyst is referred to herein asHYC1 (NiMoP/ST-5+Al₂O₃) catalyst and is a catalyst according to thepresent invention.

EXAMPLE 3

Table 4 shows the results obtained with 10 cc of HYC1 catalyst preparedaccording to Example 2. The catalyst was evaluated according to theprocedure described in Example 1.

TABLE 4 Hydroconversion Feedstock Catalyst, FCC C9+ Naphtha HYC1NiMoP/ST-5 + Al₂O₃ from Amuay Operation Conditions LSHV, h¹ 1 1 1 1Pressure, psig 600 600 600 600 Temperature, ° C. 300 320 340 360 Hours 710 14 18 Product Quality Sulfur, ppm 261 136 80 74 1930 Nitrogen, ppm 3944 22 8 186 Olefins, wt % 3.659 3.454 3.347 3.256 8.610 i-p/n-p ratio4.10 3.56 3.45 3.30 3.14 Average Molecular weight 119.2 112.5 106.2137.5 of n-paraffins HDS, wt % 86.5 93.0 95.9 96.2 HDN, wt % 79.0 76.488.0 95.5

It can be seen that the HYC1 catalyst has a moderate activity inhydrodesulfurization (HDS) which increases (between 86.3 and 96.2) asthe temperature increases from 300 to 360° C. The HDS activity is lessthan that obtained with the Commercial catalyst (HDT1), especially atlow temperatures, while they are similar at high temperatures. Theolefins hydrogenation (HDO) in this catalyst was moderate, maintainingapproximately 40 wt % of the initial olefin content. The averagemolecular weight of n-paraffins is lower in the HYC1 catalyst ascompared with HDT1 catalyst, and it decreases as the temperatureincreased from 300 to 360° C. This indicates that the HYC1 catalyst hasa very important acid function. Another important aspect is theisoparaffins/n-paraffins ratio, which is substantially higher when usingthe HYC1 catalyst.

This example demonstrates that even though the activity in HDS of thiscatalyst is slightly reduced as compared to HDT1 catalyst at lowtemperatures, the HDS activity is very similar at high temperatures,with the advantage that the HYC1 catalyst has a lower HDO, a substantialreduction of the average molecular weight of n-paraffins, and a higherisoparaffins/n-paraffins ratio, which do not occur with the HDT1catalyst. With the HDT1 catalyst, the hydrogenation of thesehydrocarbons leads to the reduction of key components which otherwisehelp to obtain high octane numbers, furthermore HDT1 catalyst does notexhibit the very important acid function to generate other keycomponents useful to avoid octane loss.

EXAMPLE 4

Following the procedure of Example 2, a similar catalyst was prepared,using alumina and the same ST-5 zeolite having a relation Si/Al of 11.7,but the impregnation was carried out using cobalt instead of nickel(from cobalt nitrate). The content of the elements, cobalt, molybdenum,phosphorus, in the resulting catalyst (referred to as HYC2) is exhibitedin Table 5.

TABLE 5 Chemical Analysis (% weight) Molybdenum 8.10 Phosphorus 1.30Cobalt 2.70 Mo + Co + P 12.10 Co/Co + Mo (atomic) 0.35

EXAMPLE 5

A similar procedure to Example 1 was used to evaluate the HYC2 catalyst.The difference was that 30 cc of catalyst was activated varying thetemperature as follows: 150° C. (1 hours), 240° C. (1 hours), 280° C. (2hour), and that three different naphthas were used, one HVN naphtha, ahydrotreated C9+FCC (to which dimethyldisulfur was added to maintain theCoMoP phase of the sulfured catalyst), and non-hydrotreated naphthaC9+of FCC. The feed characteristics are indicated together withoperation conditions and results in Table 6.

TABLE 6 Feedstock FEEDSTOCK-1 FEEDSTOCK-2 FEEDSTOCK-3 FEEDSTOCK-4Sulfur, ppm 588 (DMDS) 633 (DMDS) 1780 2010 Total Nitrogen, ppm 5 5 207130 Composition, % wt Olefins, % wt 0 1.975 8.127 7.984 i-p/n-p ratio1.59 4.51 3.47 — RON Motor 87.4 92.6 MON Motor 75.9 81.5 ROAD 81.7 87.1Feedstock 1 2 2 3 3 3 3 4 Operation Conditions Pressure, psig 600 600600 600 600 600 600 600 Temperature, ° C. 280 280 300 300 320 360 370370 Ratio H₂/HC,N/v/v 400 400 400 400 400 400 400 400 LHSV, h⁻¹ 1 1 1 11 1 1 1 HOS 15 23 29 33 36 39 75 105 Product Quality Sulfur, ppm — — —181 60 50 33 39 Nitrogen, ppm <5 <5 Olefins, wt % 0 1.877 1.205 2.3882.144 2.003 1.815 1.715 i-p/n-p ratio 2.35 6.01 6.00 4.74 4.31 4.20 4.00— RON — — — — — — 86.5 91.7 MON — — — — — — 77.2 80.8 ROAD — — — — — —81.9 86.3 HDS, % wt N/A N/A N/A 89.8 96.6 97.2 98.2 98.1 HDO, % wt N/AN/A N/A 70.6 73.6 75.4 77.7 78.5 Δ RON — — — — — — −0.9 −0.9 Δ MON — — —— — — 1.3 −0.7 Δ ROAD — — — — — — 0.2 −0.8

As shown in Table 6, this example demonstrates that the HYC2 catalyst isable to efficiently hydrodesulfurize the non-hydrotreated FCC naphthareaching an HDS activity between 96.6 and 98.2%, with a moderate HDOactivity, between 320° C. and 370° C., and with almost no loss in octanenumber. With the HYC2 catalyst, only a loss of 0.9 in RON resulted, anda gain in MON (up to 1.3 with feedstock 3) was also observed.

In the case of HVN naphtha, (heavy virgin naphtha, Feed 1), the catalystis able to raise the isoparaffins/normal paraffins ratio from 1.59 to2.35, and in the case of hydrotreated FCC naphtha (Feed 2), from 4.51 to6.01. This increase of isoparaffins/normal paraffins ratio also happenswith FCC naphtha that is not hydrotreated.

EXAMPLE 6

A catalyst (HYCPA1) corresponding to U.S. Pat. No. 5,576,256 wasobtained to be evaluated. The chemical composition and some physicalproperties of the MFI zeolite used to prepare this catalyst, arepresented in Table 7.

TABLE 7 Chemical Composition of MFI Zeolite nA1 Crystal Superf. MFIZeolite Chemical Formula (10²⁰/g) size μm Area m²/gNa_(0.05)H_(5.15)Al_(5.2)Si_(90.8)O₁₉₂ 5.4 2-3 411 *nA1(10²⁰/g): numberof rated Bronsted sites (totals) calculated from the chemical formula

The content of elements in the HYCPA1 catalyst is exhibited in Table 8.

TABLE 8 Percentage of content of metals in HYCPA1 catalyst ChemicalAnalysis % weight Molybdenum 4.30 Phosphorus 0.71 Cobalt 2.10 Gallium0.41 Chromium 0.06 Mo + Co + P 7.10 Co/Co + Mo (atomic) 0.45

The catalytic evaluation procedure of Example 1 was used so as toevaluate 30 cc of HYCPA1 catalyst. The results and the operationconditions used to evaluate this catalyst are shown in Table 9.

TABLE 9 Results of the HYCPA1 catalytic system evaluation FeedstockFEEDSTOCK-1* FEEDSTOCK-2** FEEDSTOCK-3 FEEDSTOCK-4 Sulfur, ppm 588(DMDS) 633 (DMDS) 1780 2010 Total Nitrogen, ppm 5 5 207 130 Olefins, wt.% 0 1.975 8.127 7.984 i-p/n-p ratio 1.59 4.51 3.47 — RON — — 87.4 92.6MON — — 75.9 81.5 ROAD — — 81.7 87.1 Feedstock 1 2 3 3 3 3 4 Operationconditions Pressure, psig 600 600 600 600 600 600 600 Temperature, ° C.280 300 300 320 360 370 370 Ratio H₂/HC,N/v/v 400 400 400 400 400 400400 LHSV, h⁻¹ 1 1 1 1 1 1 1 Hours 32 48 56 59 62 107 131 Product QualitySulfur, ppm — — 105 75 47 196 459 Nitrogen, ppm — — 25 20 11 — —Olefins, wt % 0 0.187 0.373 0.567 0.581 2.186 2.642 i-p/n-p ratio 2.215.18 4.19 4.11 3.87 3.77 — RON — — — — — 82.5 89.1 MON — — — — — 74.079.0 ROAD — — — — — 78.3 84.1 HDS, % wt N/A N/A 94.1 95.8 97.4 89.0 77.2HDO, % wt N/A N/A 95.4 93.0 92.9 73.1 66.9 Δ RON — — — — — −4.9 −3.5 ΔMON — — — — — −1.9 −2.5 Δ ROAD — — — — — −3.4 −3.0 *HVN and **HCNHydrotreated

As shown in Table 9, this example demonstrates that the HYCPA1 catalystdoes not maintain the HDS activity constant with FCC naphtha that isnon-hydrotreated, since the HDS activity which varies between 94.1 and87.4% in weight, between 300 and 370° C., experiences an importantdeactivation, decreasing to 77.2% at 370° C., and on the other side,presents a significant loss of octane number with feedstock 3 (RON=−4.9and MON=−1.9), and with feedstock 4 (RON=−3.5 and MON=−2.5).

In the case of HVN (feed 1), this catalyst is able to efficientlyincrease the isoparaffins/normal paraffins ratio from 1.59 to 2.21, andin the case of hydrotreated FCC naphtha (Feed 2) from 4.51 to 5.18.Similar results are demonstrated with the FCC naphtha non-hydrotreated(Feed 3). The increase, of isoparaffins/normal paraffins ratios arelower than those presented by HYC2 catalyst.

Note that the HYCPA1 catalyst showed some deactivation after 107 hoursof operation time, as can be observed clearly from the HDS activitydemonstrated from 97.4 wt % at 360° C., 62 hours, to 89.0 wt % at 370°C., 107 hours, and the HDO activity decreased too.

EXAMPLE 7

In this example, average molecular weight was measured for resultingproduct obtained using HYC2 catalyst of Example 5, HYCPA1 catalyst ofExample 6 and also with the conventional HDT1 catalyst. Averagemolecular weight and i-p/n-p ratio was measured of the product forprocesses carried out at different temperature. The results and theoperation conditions used to evaluate the catalysts are shown in Table10.

TABLE 10 Feedstock molecular weights and i-p/n-p ratio against productsof the evaluation of HYC2, HYCPA1 and HDT-1 catalyst with nonhydrotreated C9+ FCC naphthas of Amuay FEEDSTOCK PROPERTIES FEEDSTOCK 3FEEDSTOCK 3* Sulfur, ppm 1780 1930 Nitrogen, ppm 207 186 AverageMolecular Weight Paraffins 136.5 137.0 Isoparaffins 138.7 140.1Naphthenes 129.8 126.7 Aromatics 129.3 128.2 i-p/n-p ratio 3.47 3.14Feedstock 3 3 3 3 3 3 3* 3* 3* OPERATION CONDITIONS Pressure, psig 600600 600 600 600 600 600 600 600 Temperature, ° C. 300 320 360 300 320360 300 320 360 LHSV, h⁻¹ 1 1 1 1 1 1 1 1 1 RESULTS HYC2 HYCPA1 HDT1Average Molecular Weight Paraffins 130.4 116.9 102.1 133.3 131.6 121.5136.0 135.8 135.7 Isoparaffins 126.3 125.8 119.6 135.6 131.6 132.8 134.9134.8 134.3 Naphthenes 122.6 123.5 122.3 122.4 123.9 122.8 121.9 121.6122.0 Aromatics 129.4 128.2 127.8 128.2 129.6 129.3 128.9 128.9 128.8i-p/n-p ration 4.74 4.31 4.20 4.19 4.11 3.87 3.10 3.12 3.12

This table demonstrates that the HYC2 catalyst in accordance with thepresent invention is more active in the process of molecular weightreduction, especially of the n-paraffins, and the i-p/n-p ratioincreases. The HYCPA1 and finally the commercial HDT1 catalyst are notas active in these functions. In this regard, the HYC2 catalyst containsMFI zeolite having an Si/Al ratio of 11.7, the HYCPA1 has an MFI zeolitehaving an Si/Al ratio of 18, and finally the commercial catalyst HDT1does not contain zeolite, but only alumina. As an example, FIG. 2illustrates the evolution of the average molecular weight of then-paraffins with the operation temperature used to evaluate thedifferent catalysts.

In FIG. 2, it can be observed clearly that HYC2 catalyst has morecapacity than the HYCPA1 and HDT1 catalysts to reduce the n-paraffinsaverage molecular weight in an operating temperature period between 300and 360° C. in the process of a non-hydrotreated C9+(FCC) naphtha comingfrom the Amuay Refinery. Note that he HDT1 is much less efficient sinceit maintains practically the value of said molecular weight almostconstant with the temperature. This activity of the HYC2 catalyst isparticularly desirable since reduction of average molecular weight ofn-paraffins, and increases of i-p/n-p ratio, serve to improve octanevalues of the hydrocarbon.

EXAMPLE 8

A similar catalytic evaluation procedure was used as in Example 5 so asto evaluate 30 cc of HDT1 catalyst using non-hydrotreated FCC naphtha.The results are compared in Table 11 with the results obtained withHYCPA1 catalyst of Example 6 and with the HYC2 catalyst (Example 5) inaccordance with the present invention. The HYC2 catalyst is able toalmost maintain the octane number of the Feedstock: −0.9 in RON and anincrease in MON of 1.3 for Feedstock 3 and a small loss of 0.7 withFeedstock 4, while the HYCPA1 catalyst loses octane value significantly:RON=−4.9 and MON=−1.9 with Feedstock 3, and RON=−3.5 and MON=−2.5 withFeedstock 4, and still more losses occur in the case of the commercialHDT1 catalyst: RON=−6.1 and MON=−3.1.

Finally, the HYC2 catalyst is also capable of efficiently removing thesulfur as well as the HDT1 commercial catalyst, reaching high HDSactivities of 96.6 wt % to 320° C. (Table 11) and more than 98% wt to370° C.

TABLE 11 FEEDSTOCK FEEDSTOCK 3 FEEDSTOCK 4 FEEDSTOCK 5 Total Sulfur,1780 2010 2080 ppm Nitrogen, ppm 207 130 203 Olefins, wt % 8.127 7.9848.775 i-p/n-p ratio 3.47 — — RON 87.4 92.6 89.1 MON 75.9 81.5 79.3 ROAD81.7 87.1 84.2 FEEDSTOCK 3 3 4 4 5 OPERATION CONDITIONS Pressure, psig600 600 600 600 600 Temperature, ° C. 370 370 370 370 320 LHSV, h⁻¹ 1 11 1 1 RESULTS HYC2 HYCPA1 HYC2 HYCPA1 HDT1 Sulfur, ppm 33 196 — 459 <20Nitrogen, ppm <5 — <5 — <5 Olefins, wt % 1.815 2.186 1.715 2.642 0.485i-p/n-p ratio — 3.77 — — — RON 86.5 82.5 91.7 89.1 83.0 MON 77.2 74.080.8 79.0 76.2 Δ RON −0.9 −4.9 −0.9 −3.5 −6.1 Δ MON 1.3 −1.9 −0.7 −2.5−3.1 HDS, wt % 98.2 89.0 — 77.2 99.0 HDN, wt % >96.2 — >96.2 — >97.5HDO. wt % 77.7 73.1 78.5 66.9 94.5

EXAMPLE 9

The catalytic evaluation procedure of Example 5 was used, employing aunit having a higher capacity reactor (50-150 cc), so as to evaluate 100cc of the HYC2 catalyst over a long period of time with differentfeedstocks having different nitrogen and sulfur content, differentoctane values and different compositions. The procedure used is asfollows.

100 cc of dried catalyst is diluted with a 1:1 by volume amount ofsilicon carbide (carborundum), and was fed to a reactor having a lengthof 1.2 m (T/T) and an internal diameter of 2.5 cm. In order to avoidpolymerization reactions and gum formation, a 45 cc bed of commercialHDT catalyst (HDT1) is positioned at the top of the reactor (180-200°C.) allowing hydrogenation of the compounds which normally areprecursors to the formation of gums.

The catalyst is presulfurized utilizing a presulfurizing feed, by adding70 cc of carbondisulfide for every 5 liter of hydrotreated naphtha. Theschedule of presulfurization of the catalyst, after drying andcalcination, is as follows:

Operation Downflow Catalyst Volume 100 cc diluted 1:1 vol/vol with SiCHydrogen Pressure 400 psig Presulfurizing Feed Hydrotreated naphthamixture (5 lts) + CS2 (70 cc) Spatial Velocity 2.0 v/v/h Relation H₂/HC300 Nv/V Presulfurizing Feed Flow 144.6 gr/hr Hydrogen Flow 6.5 gr/hrTemperatures 150° C. (maintaining mixture pumping for 1 hour) 240° C.(maintaining mixture pumping for 1 hour) 280° C. (maintaining mixturepumping for 2 hour) T Increment Speed 30° C./h

Once activation is completed, evaluation tests of the catalyst werebegun starting with a “white” condition using hydrotreated naphtha(without sulfur or nitrogen content) at standard hydrotreatmentconditions (500-600 psi and 290° C.). This establishes a starting pointof the test.

Table 12 set forth below indicates the various naphthas used in thistest, as well as operating conditions and results obtained in terms ofHDS, octane values, liquid hydrocarbon yields and the like for 711 hoursof operation at different rates of severity.

TABLE 12 Temperature LHSV Time on stream Yield HDS Feed ° C. h⁻¹ hours %(*) ΔMON N/A HVN 290 1.5 411 84.9 19.7 N/A <5 ppm T.Nit., 588 ppm Sulf.FCC C7+ 360 3 190 98.2 0.3 97.9 48 ppm. T.Nit, 1600 ppm Sulf. 12.5% byweight of Olefins FCC C7+ 360 3 302 98.8 −0.2 99 48 ppm. T.Nit, 1600 ppmSulf. 12.5% by weight of Olefins FCC C7+ 360 3 413 98.8 −0.4 98.6 48ppm. T.Nit, 1600 ppm Sulf. 12.5% by weight of Olefins FCC C7+ 360 3 59599.7 0.4 99.3 48 ppm. T.Nit, 2210 ppm Sulf. 10.8% by weight of OlefinsFCC C7+ 360 4 642 99.6 0.1 96.4 48 ppm. T.Nit, 2210 ppm Sulf. 10.8% byweight of Olefins FCC C7+ 370 4 674 99.2 −0.1 98.9 48 ppm. T.Nit, 2290ppm Sulf. 10.8% by weight of Olefins FCC C7+ 370 4 711 99.6 0.2 98.6 138ppm. T.Nit, 2290 ppm Sulf. 9.5% by weight of Olefins

The stability test clearly demonstrates that the HYC2 catalyst of thepresent invention efficiently processes various types of naphthas havingdifferent content of nitrogen and sulfur, all the while maintaining anexcellent HDS activity, and a high liquid hydrocarbon yield, and alsowhile maintaining octane values as desired. This activity was maintainedthrough severe operating conditions including 370° C., LHSV of 4 h⁻¹,and H₂/HC of 250 N vol/vol.

EXAMPLE 10

The catalytic evaluation procedure of Example 9 was used, employing aunit having 3 reactors in parallel (50-150 cc capacity), so as toevaluate, simultaneously, the following three catalysts: 100 cc of HYC2,100 cc of HDT1 and 100 cc of HDT2 (commercial catalyst consisting ofCoMoP/Al₂O₃), with a feedstock having 17 wt % olefins, 1260 wt ppm ofsulfur and 80 wt ppm of nitrogen (Table 13).

TABLE 13 Feedstock & FCC Naphtha Total sulfur, ppm 1260 Total nitrogen,ppm 80 RON 94.1 MON 81.2 ROAD 87.7 PONA, wt % Paraffins 19.5 Olefins17.2 Naphthenes 10.8 Aromatics 50.9 No identified/C13⁺ 1.6

The operation conditions of this test were varied as follows:

Temperature, ° C. 260-350 Pressure, psig 250-500 LHSV, h⁻¹  3-8 H₂/Feedstock, N v/v 110-250

The objective of this test was to compare the performance in HDS/octaneloss of the HYC2 catalyst with different conventional hydrotreatingcatalysts at different operation conditions, especially at low severity.

FIG. 3 illustrates the Delta Octane or octane loss (ROAD) as a functionof the HDS activity for different catalysts. This figure shows the HDSactivity variation between 88.0 wt % and 99.0 wt % for the conventionalhydrotreating catalysts, and between 92.0 and 99.0 wt % for the HYC2catalyst. The octane loss decreases when the HDS activity is lowered.This octane loss is higher for the conventional hydrotreating catalysts.

For Example, at 98.0 wt % of HDS activity, the octane loss is about 5.8with conventional hydrotreating catalysts versus about 3.3 obtained withthe HYC2 catalyst. When the HDS activity is reduced to 92.0 wt %, thedifference in octane loss is still higher: 5.5 versus 1.1. Regardingthese results, the HDO activities were 89.0 and 46.0 wt % for octaneloss of 5.5 and 1.1, respectively.

This example demonstrates that HYC2 catalyst maintains octane values ata maximum as compared to conventional catalysts. The HYC2 catalyst tendsto retain more olefins in the product, compared to the conventionalhydrotreating catalysts, at similar HDS activity.

The previous examples and this example demonstrate that the HYC2catalyst has a variable selectivity according to the operationconditions used in the process: hydroconversion at high severity, highHDS/HDO ratio at low severity and both catalytic properties at mildseverity. These catalytic properties can be used adequately according tonaphtha composition to be processed.

It should be appreciated that a catalyst has been provided whichadvantageously has HDS and HDN activity, without extreme sensitivity tonitrogen, and which maintains the octane values of the feed.

This invention may be embodied in other forms or carried out in otherways without departing from the spirit or essential characteristicsthereof. The present embodiment is therefore to be considered as in allrespects illustrative and not restrictive, the scope of the inventionbeing indicated by the appended claims, and all changes which comewithin the meaning and range of equivalency are intended to be embracedtherein.

1. A process for hydroconversion of hydrocarbon feed, comprising thesteps of: providing a hydrocarbon feed having an initial sulfur content;providing a hydroconversion catalyst comprising a support comprising amixture of zeolite and alumina, wherein said support comprises betweenabout 10 and about 90% wt of said zeolite and between about 90 and about10% wt of said alumina, said zeolite is MFI zeolite having an Si/Alratio of between about 1 and about 20; and (2) a metal active phase onsaid support and comprising a first metal selected from group 6 of theperiodic table of elements, a second metal selected from the groupconsisting of group 8, group 9 and group 10 of the period table ofelements, and a third element selected from group 15 of the periodictable of elements, wherein said metal active phase contains at leastabout 1% (wt) of said first metal, at least about 0.5% (wt) of saidsecond metal, and at least about 0.2% (wt) of said third element;exposing said feed to said catalyst under hydroconversion conditions soas to provide a product having a final sulfur content less than saidinitial sulfur content.
 2. The process according to claim 1, whereinsaid hydrocarbon feed has an initial molar ratio of iso-paraffins ton-paraffins, and said product has a final molar ratio of iso-paraffinsto n-paraffins which is greater than said initial molar ratio.
 3. Theprocess according to claim 1, wherein said hydrocarbon feed has aninitial molecular weight of n-paraffins, and said product has a finalmolecular weight of said n-paraffins which is less than said initialmolecular weight.
 4. The process according to claim 1, wherein saidfirst metal is molybdenum.
 5. The process according to claim 1, whereinsaid second metal is selected from the group consisting of nickel,cobalt and mixtures thereof.
 6. The process according to claim 1,wherein said third element is phosphorus.
 7. The process according toclaim 1, wherein said hydroconversion conditions include a temperatureof between about 230 and about 450° C.
 8. The process according to claim1, wherein said MFI zeolite is ST-5 zeolite.
 9. The process according toclaim 1, wherein said feed contains nitrogen in an amount of at leastabout 1 ppm.
 10. The process according to claim 1, wherein said exposingstep is carried out in a single reactor.
 11. The process according toclaim 1, wherein said exposing step is carried out in at least tworeactors using different configurations.
 12. The process according toclaim 1, wherein said feed is a naphtha feedstock.
 13. The processaccording to claim 1, wherein said Si/Al ratio is less than about 15.14. The process according to claim 1, wherein said Si/Al ratio is lessthan about 12.